EP1094049B1 - Verfahren zur Synthese von Kohlenwasserstoffen aus Synthesegas in Gegenwart von einer, in einer flüssigen Phase dispergierten Raney Metalllegierung - Google Patents

Verfahren zur Synthese von Kohlenwasserstoffen aus Synthesegas in Gegenwart von einer, in einer flüssigen Phase dispergierten Raney Metalllegierung Download PDF

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Publication number
EP1094049B1
EP1094049B1 EP00402496A EP00402496A EP1094049B1 EP 1094049 B1 EP1094049 B1 EP 1094049B1 EP 00402496 A EP00402496 A EP 00402496A EP 00402496 A EP00402496 A EP 00402496A EP 1094049 B1 EP1094049 B1 EP 1094049B1
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EP
European Patent Office
Prior art keywords
catalyst
process according
liquid phase
weight
metals
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP00402496A
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English (en)
French (fr)
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EP1094049A1 (de
Inventor
François Hugues
Magalie Roy-Auberger
Marie-Claire Marion
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IFP Energies Nouvelles IFPEN
Eni SpA
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IFP Energies Nouvelles IFPEN
Eni SpA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J25/00—Catalysts of the Raney type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons
    • C07C1/063—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons the organic compound being the catalyst or a part of the catalyst system
    • C07C1/066—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons the organic compound being the catalyst or a part of the catalyst system used for dissolving, suspending or transporting the catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2525/00—Catalysts of the Raney type

Definitions

  • the present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising CO- (CO 2 ) -H 2 (ie a mixture comprising carbon monoxide and hydrogen and optionally CO 2 , commonly known as syngas).
  • This process for the conversion of synthesis gas includes the use of a particular catalyst, usually called a Raney catalyst.
  • This type of catalyst is essentially constituted by a metal alloy comprising at least at least 60% by weight of at least one metal chosen from the metals of groups 8, 9 or 10. It may however include other constituents detailed below.
  • this catalyst is used in a reactor operating in liquid phase, preferably a slurry reactor, i.e. a three-phase reactor operating with the solid catalyst suspended in a liquid phase and in the presence of a gas phase. More preferably, the catalyst is used in a slurry bubble column type reactor.
  • synthesis gas can be converted into hydrocarbons in the presence of catalysts containing transition metals. This conversion, carried out at high temperature and under pressure, is known in the literature under the name of Fischer-Tropsch synthesis.
  • metals from groups 8, 9 or 10 of the periodic table of elements such as for example iron, ruthenium, cobalt and nickel catalyze the transformation of mixtures CO- (CO 2 ) -H 2 (that is ie a CO-H 2 mixture optionally comprising CO 2 , called synthesis gas) in liquid and / or gaseous hydrocarbons.
  • Raney's cobalt or nickel type catalysts have long been known from those skilled in the art as catalysts which can be used in hydrogenation reactions of organic compounds.
  • the Raney process describes how to prepare a porous and active metal catalyst by first preparing a bimetallic alloy where one of the two metals can be extracted for give a non-soluble porous material which is active in catalysis.
  • Raney catalyst is a catalyst formed of insoluble metal, well known in the art. Raney process and which typically can be nickel, cobalt, copper or iron.
  • Raney catalysts are generally produced from an alloy of the catalytic metal considered (eg nickel or cobalt) with aluminum.
  • the alloy is reduced in powder, then the aluminum is removed by attack using a sodium hydroxide solution, making thus appears a finely divided metal, which has a specific surface generally between 10 and 150 m2 / g, and more preferably between 10 and 100 m2 / g. Under this forms the metal obtained (nickel or cobalt) has a high adsorption capacity of hydrogen, hence its interest in catalysis.
  • Patent EP 0 648 534 describes the preparation of Raney metals shaped for their use in a fixed bed. These metals can be used as a hydrogenation catalyst organic compounds.
  • Patent EP 0 450 861 describes the use of a slurry phase process with a cobalt-based catalyst supported on TiO 2 .
  • the use of a bubble column in which the catalyst is suspended in a liquid phase makes it possible to obtain at least the productivity of a reactor in a fixed bed, and the selectivity of a perfectly stirred reactor.
  • the present invention relates to a process for the synthesis of hydrocarbons from a mixture comprising carbon monoxide and hydrogen CO-H 2 , optionally carbon dioxide CO 2 , in the presence of a catalyst essentially consisting of a metallic alloy comprising at least one metal chosen from the metals of groups 8, 9 or 10, preferably iron or cobalt, used in suspension in a liquid phase in a reactor operated most often in the presence of three phases: a liquid phase , a gas phase and a solid phase at least partly constituted by the catalyst (slurry reactor).
  • the catalyst used in the process according to the invention essentially consists of a metal alloy containing at least about 60% by weight of at least one metal chosen from metals of groups 8, 9 or 10, preferably at least 70% by weight of at least one metal chosen from the metals of groups 8, 9 or 10, and very preferably at least 80% weight of at least one metal chosen from the metals of groups 8, 9 or 10.
  • the catalyst has a grain size generally less than about 700 microns, of preferably less than about 250 microns, more preferably between 1 and 150 microns, and very preferably between 10 and 80 microns, for a optimal use of the reactor operating in the liquid phase, in particular when it is a slurry bubble column type reactor.
  • the catalyst used in the process according to the invention can be prepared using any technique known to those skilled in the art for preparing Raney alloys.
  • it can be prepared using the methods described in patents US-A-1,628,190, US-A-1,915,473, US-A-2,977,327 and EP-A- 0,648,534. These methods may optionally be modified using the knowledge of a person skilled in the art, in order to obtain the desired characteristics.
  • One of the preferred methods of preparing this catalyst consists in the formation of a alloy between the two metals, for example cobalt and aluminum, at high temperature (1300 ° C), shaping by atomization, then activation with a hydroxide solution sodium to give, after separation of the sodium aluminate solution, the catalyst ready to use.
  • the catalyst can moreover optionally contain at least one additional element chosen. among the alkali metals or the metals of groups 4, 5, 6, 7, 8, 9, 10 or 11 of the new periodic classification.
  • This additional element is preferably chosen from the group consisting of titanium, zirconium, iron, ruthenium, molybdenum, tungsten and tantalum.
  • the content by weight of an additional element relative to the total weight of catalyst is preferably between 0 and about 12% by weight, more preferably between 0.01 and 10% by weight, very preferably between 0.1 and 5% by weight.
  • additional elements can be introduced at the same time as the metal or metals chosen from elements from groups 8, 9 or 10, or in at least one subsequent step.
  • the present invention relates to a process for the conversion of synthesis gas, using a catalyst whose performance is particularly stable, and which leads to a mixture of essentially linear and saturated hydrocarbons generally containing at least 50% by weight of C5 + hydrocarbons and generally less than 20% by weight of methane, preferably less than 15% by weight of methane relative to all of the hydrocarbons formed.
  • This process is operated under a total pressure usually between 0.1 and 15 MPa, preferably between 1 and 10 MPa, a temperature generally between 150 ° C and 350 ° C, preferably between 170 ° C and 300 ° C.
  • the volumetric speed hourly is usually between 100 and 2000 volumes of synthesis gas per volume of catalyst per hour and preferably between 400 and 5000 volumes of synthesis gas by volume of catalyst and per hour.
  • the H2 / CO molar ratio of synthesis is usually between 1: 2 and 5: 1, preferably between 1.2: 1 and 2.5: 1
  • the conditions for using said catalysts in the process according to the invention are usually the following:
  • the catalyst is generally used directly in the reaction, without treatment beforehand, and in the form of a fine calibrated powder (particle size less than about 700 approximately microns) in the presence of a liquid phase.
  • the liquid phase can consist of at least one hydrocarbon having at least 5 carbon atoms per molecule, of preferably at least 10 carbon atoms per molecule.
  • this phase liquid consists essentially of paraffins, and more preferably of paraffins from a Fischer-Tropsch synthesis. In general we will choose a cut whose the initial and final boiling points are such that it is within the range of kerosene or diesel.
  • the catalyst is suspended in an inert solvent, for example a paraffinic fraction comprising at least one hydrocarbon having at least 5 carbon atoms per molecule, preferably at least 10 carbon atoms per molecule.
  • an inert solvent for example a paraffinic fraction comprising at least one hydrocarbon having at least 5 carbon atoms per molecule, preferably at least 10 carbon atoms per molecule.
  • This type of implementation requires a separation of the catalyst and the products of reaction. It can be carried out in the reactor or outside the reactor.
  • filter elements are interposed on the evacuation line of the reactor products, and keep all the catalyst in the reactor, as described in patent application EP-A-0 609 079.
  • the suspension (slurry) is generally put into circulation, by means for example a pump.
  • Various means of separation can be used, as well as is indicated in patent application WO 97 / 31,693.
  • the catalyst used in the process according to the invention is that its high metal content leads to high density and efficient separation of the most large part of the catalyst, for example by means of simple decantation.
  • the catalyst employee most generally has an apparent density greater than 1.2 kilograms per (kg / l), preferably greater than 1.5 kg / l, and very preferably more than 1.8 kg / l.
  • the invention therefore relates to a process for the synthesis of hydrocarbons from synthesis gas, in the presence of a catalyst essentially consisting of an alloy Raney metal dispersed in a liquid phase, in which the catalyst comprises at least at least 60% by weight of at least one metal chosen from the metals of groups 8, 9 or 10.
  • said metal is chosen from iron or cobalt.
  • the catalyst of the process according to the invention can also comprise at least one element additional chosen from alkali metals and metals of groups 4, 5, 6, 7, 8, 9, 10 or 11.
  • this additional element is chosen from the group consisting of titanium, zirconium, iron, ruthenium, molybdenum, tungsten and tantalum.
  • Weight content of the additional element relative to the total weight of catalyst is between 0 and about 12% by weight, preferably between 0.01 and 10% by weight. And more preferably between 1% and 5% by weight.
  • the catalyst has a grain size less than about 700 microns.
  • the liquid phase used in the process according to the invention is a cut kerosene or diesel from the Fischer-Tropsch synthesis.
  • the catalyst can optionally be modified by means of a pretreatment before introduction into the reactor, for example a reduction carried out at a temperature between 100 ° C and 600 ° C, at a pressure between 0.1 and 10 MPa and at a hourly volumetric speed between 100 and 40,000 volumes of mixture per volume of catalyst per hour.
  • the catalyst is used in a reactor operating in the liquid phase of type three-phase bubble column (slurry bubble column).
  • Example 1 (according to the invention): catalyst A
  • a catalyst A of the Raney cobalt type sold by the company Degussa under the reference B2112Z, is in the form of a pre-activated powder and stored in water, protected from air.
  • the metal powder has a particle size between 1 and 130 microns.
  • the metal cobalt content of catalyst A is greater than about 95% by weight.
  • a catalyst B of the Raney cobalt type sold by the company Degussa under the reference Cobalt beta-1000, is in the form of pellets of size 4 millimeters by 4 millimeters. Wet grinding of these pellets which are stored in water is carried out so as to reduce the particle size of the catalyst while keeping it away from air.
  • the recovered powder has a particle size between 1 and 130 microns.
  • the metal cobalt content of catalyst B is approximately 60% by weight.
  • a catalyst C of formula Co / Al2O3 is prepared by impregnating an alumina powder with a specific surface of 180 m 2 / g.
  • This support is in the form of a powder with a particle size between 10 and 150 microns. After impregnation, the support is dried and calcined at 400 ° C. The final cobalt content is 12.5%.
  • the catalysts described in Examples 1 and 2 are used in a column with three-phase bubble with internal diameter 50 mm and height 1500 mm.
  • This column is also equipped with a synthesis gas intake manifold, at the bottom of the column, a tube for drawing off the suspension above the liquid level, a tube for reinjection of the suspension at the bottom of the column, and of a circulation loop comprising a degasser, a decanter, and a pump.
  • the catalyst is separated from the liquid products by means of the decanter, the catalyst content in the liquid after settling is less than 100 ppm by weight.
  • Catalyst C is used under the same conditions as catalyst A. It leads to a CO conversion of 61%, and a selectivity to C5 + hydrocarbons of 72%. After decantation in the same apparatus, the liquid obtained contains 0.15% by weight of catalyst, this which requires filtration after settling.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (10)

  1. Verfahren zur Synthese von Kohlenwasserstoffen ausgehend von Synthesegas in Gegenwart eines Katalysators, der aus einer Raney-Metall-Legierung besteht, die in einer Flüssigphase dispergiert ist, in welchem der Katalysator wenigstens 60 Gewichtsprozent wenigstens eines Metalls, gewählt unter den Metallen der Gruppen 8, 9 oder 10, umfasst.
  2. Verfahren nach Anspruch 1, bei dem das Metall unter Eisen oder Kobalt gewählt wird.
  3. Verfahren nach einem der Ansprüche 1 oder 2, im übrigen wenigstens ein Zusatzelement umfassend, das unter den Alkalimetallen und den Metallen der Gruppen 4, 5, 6, 7, 8, 9, 10 oder 11 gewählt ist.
  4. Verfahren nach Anspruch 3, bei dem das Zusatzelement aus der Gruppe gewählt ist, die gebildet wird durch Titan, Zirkonium, Eisen, Ruthenium, Molybdän, Wolfram und Tantal.
  5. Verfahren nach einem der Ansprüche 3 oder 4, bei dem der Gewichtsgehalt des Zusatzelements im Verhältnis zum Gesamt-Katalysator-Gewichtsgehalt zwischen 0 und etwa 12 Gewichtsprozent liegt.
  6. Verfahren nach einem der Ansprüche 1 - 5, bei dem der Katalysator eine Korngröße unter etwa 700 µm aufweist.
  7. Verfahren nach einem der Ansprüche 1 - 6, bei dem die Flüssigphase eine Kerosin- oder Dieselfraktion der Fischer-Tropsch-Synthese ist.
  8. Verfahren nach einem der Ansprüche 1 - 7, bei dem der Katalysator mittels einer Vorbehandlung vor Einführung in den Reaktor modifiziert wird.
  9. Verfahren nach Anspruch 8, bei dem die Vorbehandlung eine Reduktion ist, die bei einer Temperatur zwischen 100°C und 600°C, bei einem Druck zwischen 0,1 und 10 MPa und einer stündlichen Volumengeschwindigkeit zwischen 100 und 40.000 Mischungsvolumen pro Katalysator-Volumen und pro Stunde durchgeführt wird.
  10. Verfahren nach einem der Ansprüche 1 - 9, bei dem der Katalysator in einem Reaktor vom triphasischen Kolonnentyp mit Blasen eingesetzt wird.
EP00402496A 1999-10-22 2000-09-11 Verfahren zur Synthese von Kohlenwasserstoffen aus Synthesegas in Gegenwart von einer, in einer flüssigen Phase dispergierten Raney Metalllegierung Expired - Lifetime EP1094049B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9913325A FR2800065B1 (fr) 1999-10-22 1999-10-22 Procede de synthese d'hydrocarbures a partir de gaz de synthese en presence d'un alliage metallique de raney disperse dans une phase liquide
FR9913325 1999-10-22

Publications (2)

Publication Number Publication Date
EP1094049A1 EP1094049A1 (de) 2001-04-25
EP1094049B1 true EP1094049B1 (de) 2003-04-16

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EP00402496A Expired - Lifetime EP1094049B1 (de) 1999-10-22 2000-09-11 Verfahren zur Synthese von Kohlenwasserstoffen aus Synthesegas in Gegenwart von einer, in einer flüssigen Phase dispergierten Raney Metalllegierung

Country Status (5)

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US (1) US6391929B1 (de)
EP (1) EP1094049B1 (de)
CA (1) CA2323986C (de)
FR (1) FR2800065B1 (de)
NO (1) NO319776B1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030050349A1 (en) * 2001-08-31 2003-03-13 Conoco Inc. In-situ desulfurization of a feed stream in a catalytic reactor
US7375053B2 (en) * 2003-04-07 2008-05-20 W. R. Grace & Co.- Conn. Nickel and cobalt plated sponge catalysts
CN101164692B (zh) * 2006-10-20 2011-06-15 中国石油化工股份有限公司 一种钴催化剂、制备方法及其应用
US20110011772A1 (en) * 2009-07-15 2011-01-20 Stephen Raymond Schmidt Nickel and Cobalt Plated Sponge Catalysts
GB2599998A (en) * 2020-10-13 2022-04-20 Velocys Tech Ltd Catalyst
GB2599966A (en) * 2020-10-13 2022-04-20 Velocys Tech Limited Catalyst

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4422961A (en) * 1982-03-01 1983-12-27 Olin Corporation Raney alloy methanation catalyst
US5639798A (en) * 1994-12-15 1997-06-17 Wexford P.A. Syncrude Limited Partnership Process and catalyst for production of hydrocarbons
US6087296A (en) * 1998-11-05 2000-07-11 E. I. Du Pont De Nemours & Co. Raney iron catalyst and a process for hydrogenating organic compounds using said catalyst

Also Published As

Publication number Publication date
NO319776B1 (no) 2005-09-12
FR2800065B1 (fr) 2005-02-18
CA2323986A1 (fr) 2001-04-22
US6391929B1 (en) 2002-05-21
EP1094049A1 (de) 2001-04-25
CA2323986C (fr) 2010-06-01
NO20005278D0 (no) 2000-10-20
NO20005278L (no) 2001-04-23
FR2800065A1 (fr) 2001-04-27

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